Method of making coated metal articles

ABSTRACT

A method of making a coated metal article comprises (a) forming a hardcoat layer on at least a portion of a surface of a metal or metalized substrate by physical vapor deposition; (b) forming a tie layer comprising silicon, oxygen, and hydrogen on at least a portion of the surface of the hardcoat layer by plasma deposition; and (c) applying an at least partially fluorinated composition comprising at least one silane group to at least a portion of the surface of the tie layer.

CROSS REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Patent Application No. 61/247,641, filed Oct. 1, 2009, the disclosure of which is incorporated by reference herein in its entirety.

FIELD

This invention relates to a method of making durable easy clean metal articles and to durable easy clean coated metal articles.

BACKGROUND

Metal articles are used for various applications. Examples of functional metal articles include scissor blades, paper cutters and shredders, shaving blades, cutting tools, stamping dies, molds, bathroom and kitchen fixtures and appliances, automotive wheels and rims, and the like.

Metal articles, however, can be prone to contamination from handling and/or from the environment in which they are utilized. For example, scissor blades can be contaminated by adhesive residue when they are used to cut adhesive tapes; bathroom fixtures can be contaminated by soap scum and calcification; kitchen appliances and fixtures can be contaminated by cooking oils and greases; automotive wheels and rims can be contaminated by automotive oils, dirt, and grease; and cutting tools can be contaminated by machining oils and wear debris resulting from the cutting operations.

When metal articles are used for cutting or machining operations, contamination can cause the cutting edges of the articles to become dulled due to the aggressive wear created by the contaminants. In the case of stamping dies or other dies such as extrusion or molding dies, contamination can compromise the quality of the product produced by the dies. In other cases such as bathroom and kitchen fixtures and appliances, automotive wheels and rims, and the like, contamination can cause deterioration of the aesthetics or appearance of the articles.

Various methods have been used to address the problem of contamination of metal articles. For example, topical treatments or coatings that have low surface energy have been employed. Low surface energy prevents the contaminants from accumulating on the surface of metal articles. Such coatings typically include low surface energy materials such as silicone, fluorosilicones, or fluoropolymers such as polytetrafluoroethylene (PTFE), fluorinated ethylene propylene (FEP), ethylene-tetrafluoroethylene (ETFE), or the like.

While such low surface energy coatings can be effective in preventing the contamination of metal articles, they do not typically have the durability that is required for many applications.

Scissors blades, for example, are often coated with a non-stick coating comprising pigmented PTFE coatings or silicone oil. PTFE coatings are typically applied thickly and then the edges of the scissor blades are ground so that they will cut paper and/or cloth. PTFE coatings are soft and abrade quickly, however, due to flank wear on the scissors during use. This exposes the bare metal (for example, stainless steel) and allows adhesive residue to build up. Similarly, silicone oil works well initially, but wears off and is easily removed by wiping or by removing tape from the surface of the blades. After the silicone oil is removed, adhesive residue can build up on the blades.

In addition, many of the above coatings change the color or appearance of the underlying metal and diminish the luster of the metal.

SUMMARY

In view of the foregoing, we recognize that there is a need in the art for improved metal articles with surfaces that resist the accumulation of contaminants, that are easy to clean, and that remain stable over time and with use (that is, they are durable), but that maintain the luster and color of the underlying metal. In one aspect, the present invention provides a method of making a metal article.

The method comprises (a) forming a hardcoat layer on at least a portion of a surface of a metal or metalized substrate by physical vapor deposition, (b) forming a tie layer comprising silicon, oxygen, and hydrogen on at least a portion of the surface of the hardcoat layer by plasma deposition, and (c) applying an at least partially fluorinated composition comprising at least one silane group to at least a portion of the surface of the tie layer.

In another aspect, the present invention provides a coated metal article comprising (a) a metal or metalized substrate, (b) a physical vapor deposited hardcoat layer disposed on at least a portion of the metal or metalized substrate, (c) a plasma deposited tie layer comprising silicon, oxygen, and hydrogen disposed on at least a portion of the surface of the hardcoat layer, and (d) an at least partially fluorinated composition comprising at least one silane group disposed on at least a portion of the surface of the tie layer.

The method of the invention provides coated metal articles that resist the accumulation of contamination and that are easy to clean. The coated metal articles maintain the luster and color of the underlying metal while remaining clean without degrading upon repeated use. Scissors coated according to the method of the invention, for example, can maintain their easy clean (i.e., non-stick) properties after 10,000 cuts.

DETAILED DESCRIPTION

The method of the invention for making a coated metal article comprises forming a hardcoat layer on a surface of a metal or metalized substrate by physical vapor deposition.

As used herein, “metal or metalized substrate” refers to a substrate comprised of a metal and/or metal alloy, which is solid at room temperature. The metal and/or metal alloy can be selected, for example, from the group consisting of chromium, iron, aluminum, copper, nickel, zinc, tin, stainless steel, and brass, and the like, and alloys thereof. For certain of these embodiments, the metal and/or metal alloy is chromium or stainless steel. A metal substrate comprises one or more metals and/or metal alloys at a major surface and one or more metals and/or metal alloys throughout the body of the substrate. A metalized substrate also comprises one or more metals and or metal alloys at a major surface. The metalized substrate can further comprise a polymeric material, which includes one or both of thermoset and thermoplastic polymers, ceramic, glass, porcelain, as well as other materials capable of having a metalized surface.

Examples of metal or metalized substrates include, but are not limited to, kitchen and bathroom faucets, taps, handles, spouts, sinks, drains, hand rails, towel holders, curtain rods, dish washer panels, refrigerator panels, stove tops, stove, oven, and microwave panels, exhaust hoods, grills, metal wheels or rims, scissor blades, paper cutters, paper shredders, shaving blades, cutting tools, stamping dies, molds, and the like.

In preferred embodiments, the metal or metalized substrate is a cutting tool or element such as, for example, scissors, paper shredders, razor blades, knives, kitchen cutlery, butcher tools, woodworking tools, metalworking tools, and the like. The scissors can be used for a variety of applications including, for example, cutting paper, plastic, fabric, or hair. Woodworking tools can include, for example, drill bits, cutting wires, saw blades, and the like.

Forming a hardcoat layer on at least a portion of a surface of the substrate by physical vapor deposition (PVD) can be carried out using PVD methods known in the art. As used herein, “physical vapor deposition” or “PVD” refers to coating wherein at least one of the coating components is initially placed into the coating chamber in a non-gaseous form. The non-gaseous coating component is generally called the “source.” The coating chamber is typically evacuated to sub-atmospheric pressure prior to and during the coating process. Sufficient energy is applied to the source material to change it to vapor state, which vapor subsequently comes to rest in film form on the substrates, often after combining with other components. Electrostatic and/or electromagnetic fields may be used in the process of converting the source material to its vapor phase as well as to direct the coating particles toward the substrate.

Useful known PVD methods include, for example, sputtering, reactive sputtering, evaporation, reactive evaporation, ion-assisted reactive evaporation, ion-beam assisted deposition, cathodic arc evaporation, unbalanced magnetron sputtering, high power impulse magnetron sputtering (HIPIMS), thermal and electron beam (e-beam) evaporation, and the like.

PVD apparatuses known in the art such as the apparatus disclosed in U.S. Pat. No. 4,556,471 (Bergman et al.) can be utilized.

The substrate to be treated may by pre-cleaned by methods known to the art to remove contaminants that may interfere with the plasma deposition. One useful pre-cleaning method is exposure to an oxygen plasma. For this pre-cleaning, pressures in the chamber are maintained between 1.3 Pa (10 mTorr) and 27 Pa (200 mTorr). Plasma is generated with RF power levels of between 500 W and 3000 W.

A solvent washing step with an organic solvent such as acetone or ethanol or acid etch treatment may also be included prior to the exposure to oxygen plasma.

The hardcoat layer can comprise nitrides, carbides and oxides of titanium, chromium, zirconium, niobium, aluminum, mixed metal nitrides (for example, aluminum-titanium nitride, chromium-aluminum nitride, or zirconium-chromium nitride), diamond-like carbon, tetrahedral amorphous carbon, and the like. The hardcoat layer can comprise multilayer films of nitrides, carbides, oxides, and the like.

Preferred hardcoats include metal nitrides and mixed metal nitrides such as, for example, nitrides Of titanium, aluminum, chromium, tantalum, niobium, and the like. Titanium nitride, zirconium nitride, aluminum nitride, and titanium aluminum nitride are particularly useful.

Typically, the hardcoat layer is from about 0.1 to about 50 microns thick; preferably, about 0.5 to 10 microns thick.

Forming a tie layer comprising silicon, oxygen, and hydrogen on at least a portion of the surface of the hardcoat layer by plasma deposition can be carried out in a suitable reaction chamber having a capacitively-coupled system with at least one electrode powered by an RF (radio frequency) source and at least one grounded electrode, such as those described in U.S. Pat. Nos. 6,696,157 (David et al.) and 6,878,419 (David et al.).

The substrate with the hardcoat layer is either located on the powered electrode or the assembly holding the coated metal article(s) is powered with an RF power supply. The articles for coating are located in a vacuum chamber, and the chamber is evacuated to the extent necessary to remove air and any impurities. This may be accomplished by vacuum pumps at a pumping stack connected to the chamber. A source gas is introduced into the chamber at a desired flow rate, which depends on the size of the reactor, the surface area of the electrodes, and the surface area of the substrate. Precleaning of the substrate/article can be done with a suitable gas such as argon, nitrogen, or oxygen. An oxygen plasma can be particularly effective in cleaning any organic contaminants from the substrate surface before deposition of the hardcoat. During plasma deposition, the gas includes an organosilicon and/or a silane compound, and the flow rates are sufficient to establish a suitable pressure at which to carry out plasma deposition, typically 0.13 Pa to 130 Pa (0.001 Ton to 1.0 Ton). For a cylindrical reactor that has an inner diameter of approximately 55 cm and a height of approximately 20 cm, the flow rates are typically from about 50 to about 500 standard cubic centimeters per minute (sccm). At the pressures and temperatures (less than about 50° C.) of the plasma deposition, the gas remains in the vapor form. An RF electric field is applied to the powered electrode, ionizing the gas and establishing a plasma. In the RF-generated plasma, energy is coupled into the plasma through electrons. The plasma acts as the charge carrier between the electrodes. The plasma can fill the entire reaction chamber and is typically visible as a colored cloud.

The plasma also forms an ion sheath proximate the substrate/article or on the electrode. The ion sheath typically appears as a darker area around the substrate/article or electrode. Within the ion sheath, ions accelerating toward the electrode bombard the species being deposited from the plasma onto the substrate, positively impacting the adhesion and density/hardness of the deposited layer. The depth of the ion sheath normally ranges from about 1 mm to about 50 mm and depends on factors such as the type and concentration of gas used, pressure in the chamber, the spacing between the electrodes, and relative size of the electrodes. For example, reduced pressures will increase the size of the ion sheath. When the electrodes are different sizes, a larger, stronger ion sheath will form around the smaller electrode. Generally, the larger the difference in electrode size, the larger the difference in the size of the ion sheaths, and increasing the voltage across the ion sheath will increase ion bombardment energy.

The substrate comprising the hardcoat layer is exposed to the ion bombarded species being deposited from the plasma. The resulting reactive species within the plasma react on the surface of the hardcoat layer, forming another layer, the composition of which is controlled by the composition of the gas being ionized in the plasma. The species forming this layer can attach to the surface of the hardcoat layer by covalent bonds.

For certain embodiments, forming the layer comprising the silicon, oxygen, and hydrogen comprises ionizing a gas comprising at least one of an organosilicon or a silane compound. For certain of these embodiments, the silicon of the at least one of an organosilicon or a silane compound is present in an amount of at least about 5 atomic percent of the gas mixture. Thus, if a reactive gas such as oxygen or an inert gas such as argon are mixed along with the organosilicon or silane precursor, the atomic percent of silicon in the gas mixture is calculated based on the volumetric (or molar) flow rates of the component gases in the mixture. For certain of these embodiments, the gas comprises the organosilicon. For certain of these embodiments, the organosilicon comprises at least one of trimethylsilane, triethylsilane, trimethoxysilane, triethoxysilane, tetramethylsilane, tetraethylsilane, tetramethoxysilane, tetraethoxysilane, hexamethylcyclotrisiloxane, tetramethylcyclotetrasiloxane, tetraethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, hexamethyldisiloxane, and bistrimethylsilylmethane. For certain of these embodiments, the organosilicon comprises tetramethylsilane. In addition to or alternatively, for certain of these embodiments, the gas comprises the silane compound. For certain of these embodiments, the silane compound comprises one or more of SiH₄ (silicon tetrahydride), Si₂H₆ (disilane), and SiClH₃ (chlorosilane). For certain of these embodiments, the silane compound comprises SiH₄ (silicon tetrahydride).

For certain embodiments, including any one of the above embodiments, preferably the gas further comprises oxygen.

For certain embodiments, including any one of the above embodiments, the gas further comprises at least one of argon, ammonia, hydrogen, and nitrogen. Each additional gas can be added separately or in combination with each other. For certain of these embodiments, the gas further comprises at least one of ammonia, hydrogen, and nitrogen such that the total amount of the at least one of ammonia, hydrogen, and nitrogen is at least about 5 molar percent and not more than about 50 molar percent of the gas.

Plasma deposition of the layer typically occurs at a rate ranging from about 1 to about 100 nm/second. The rate will depend on conditions including pressure, power, concentration of gas, types of gases, relative size of the electrodes, and so on. In general, the deposition rate increases with increasing power, pressure, and concentration of gas, although the rate can approach an upper limit.

For certain embodiments, including any one of the above embodiments, the plasma deposition of the layer comprising the silicon, oxygen, and hydrogen is carried out for a period of time not less than about 2 seconds, not less than about 5 seconds, or not less than about 10 seconds.

For certain embodiments, including any one of the above embodiments, the plasma deposition of the layer comprising the silicon, oxygen, and hydrogen is carried out for a period of time not more than about 30 seconds, about 20 seconds, or about 15 seconds.

For certain embodiments, including any one of the above embodiments, the plasma deposition of the layer comprising the silicon, oxygen, and hydrogen is carried out for a period of time not less than about 5 seconds and not more than about 15 seconds. For certain of these embodiments, the period of time is about 10 seconds.

For certain embodiments, including any one of the above embodiments, the substrate comprising the hardcoat layer is exposed to an oxygen plasma prior to the plasma deposition of the layer comprising the silicon, oxygen, and hydrogen.

After the layer comprising the silicon, oxygen, and hydrogen is formed by plasma deposition, the surface of the layer may be exposed to an oxygen plasma to form silanol groups or to form additional silanol groups on the surface of the layer. For this post-treatment, pressures in the chamber are maintained between 1.3 Pa (10 mTorr) and 27 Pa (200 mTorr). The oxygen plasma is generated with RF power levels of between about 50 W and about 3000 W.

For certain embodiments, including any one of the above embodiments, after deposition is complete, the layer comprising the silicon, oxygen, and hydrogen is exposed to an oxygen plasma.

For certain embodiments, including any one of the above embodiments, the tie layer comprising silicon, oxygen, and hydrogen preferably further comprises carbon. The presence of the carbon can impart an increased flexibility and toughness to the layer. Useful tie layers comprising silicon, oxygen, hydrogen, and carbon include, for example, silicon dioxide, silicon monoxide, sub-stoichiometric silicon oxide, silicon carbide, silicon oxycarbide, silicon oxynitride, silicon nitride, diamond-like glass, silicon doped diamond-like carbon, and the like. Preferred ties layer comprise diamond-like glass, silicon oxide, silicon dioxide, silicon carbide, silicon nitride, silicon oxynitride, or silicon oxycarbide.

Typically, the tie layer is from about 0.001 to about 1 micron thick; preferably, from about 0.01 to about 0.1 microns thick.

After the tie layer has been formed, an at least partially fluorinated composition comprising at lease one silane group is applied to at least a portion of the surface of the tie layer. As used herein, the “at least partially fluorinated composition comprising at least one silane group” refers to at least one of polyfluoropolyether silanes, perfluoroalkyl silanes, fluorinated oligomeric silanes, or swallow-tail silanes. In one embodiment, the at least partially fluorinated composition comprising at least one silane group is a polyfluoropolyether silane. Polyfluoropolyether silanes are represented by the Formula I:

R_(f){-Q-[SiY_(3-x)(R¹)_(x)]_(y)}_(z)  I

wherein R_(f) is a monovalent or multivalent polyfluoropolyether segment; Q is an organic divalent or trivalent linking group; each Y is independently a hydrolyzable group; R¹ is an alkyl group or a phenyl group; x is 0 or 1 or 2; y is 1 or 2, and z is 1, 2, 3, or 4.

The monovalent or multivalent polyfluoropolyether segment, R_(f), includes linear, branched, and/or cyclic structures that may be saturated or unsaturated, and includes two or more in-chain oxygen atoms. R_(f) is preferably a perfluorinated group (i.e., all C—H bonds are replaced by C—F bonds). However, hydrogen or chlorine atoms may be present instead of fluorine atoms provided that not more than one atom of either hydrogen or chlorine is present for every two carbon atoms. When hydrogen and/or chlorine are present, preferably, R_(f) includes at least one perfluoromethyl group.

The organic divalent or trivalent linking group, Q, can include linear, branched, or cyclic structures that may be saturated or unsaturated. The organic divalent or trivalent linking group, Q, optionally contains one or more heteroatoms selected from the group consisting of sulfur, oxygen, and nitrogen, and/or optionally contains one or more functional groups selected from the group consisting of esters, amides, sulfonamides, carbonyl, carbonates, ureylenes, and carbamates. Q includes not less than 2 carbon atoms and not more than about 25 carbon atoms. Q is preferably substantially stable against hydrolysis. When more than one Q groups are present, the Q groups can be the same or different.

For certain embodiments, including any one of the above embodiments, Q includes organic linking groups such as —C(O)N(R)—(CH₂)_(k)—, —S(O)₂N(R)—(CH₂)_(k)—, —(CH₂)_(k)—, —CH₂O—(CH₂)_(k)—, —C(O)S—(CH₂)_(k)—, —CH₂OC(O)N(R)—(CH₂)_(k)—, and

wherein R is hydrogen or C₁₋₄ alkyl, and k is 2 to about 25. For certain of these embodiments, k is 2 to about 15 or 2 to about 10.

The hydrolyzable groups, Y, may be the same or different and are capable of hydrolyzing, for example, in the presence of water, optionally under acidic or basic conditions, producing groups capable of undergoing a condensation reaction, for example silanol groups.

For certain embodiments, including any one of the above embodiments, the polyfluoropolyether silane is of the Formula Ia:

R_(f)[Q′-C(R)₂—Si(Y′)_(3-x)(R^(1a))_(x)]_(z)  Ia

wherein:

-   -   R_(f) is a monovalent or multivalent polyfluoropolyether         segment;     -   Q′ is an organic divalent linking group;     -   each R is independently hydrogen or a C₁₋₄ alkyl group;     -   each Y′ is a hydrolysable group independently selected from the         group consisting of halogen, alkoxy, acyloxy, polyalkyleneoxy,         and aryloxy groups;     -   R^(1a) is a C₁₋₈ alkyl or phenyl group;     -   x is 0 or 1 or 2; and     -   z is 1, 2, 3, or 4.

For certain embodiments, including any one of the above embodiments of Formulas I or Ia, the monovalent or multivalent polyfluoropolyether segment, R_(f), comprises perfluorinated repeating units selected from the group consisting of —(C_(n)F_(2n))—, —(C_(n)F_(2n)O)—, —(CF(Z))—, —(CF(Z)O)—, —(CF(Z)C_(n)F_(2n)O)—, —(C_(n)F_(2n)CF(Z)O)—, —(CF₂CF(Z)O)—, and combinations thereof; Z is a perfluoroalkyl group, an oxygen-containing perfluoroalkyl group, a perfluoroalkoxy group, or an oxygen-substituted perfluoroalkoxy group, each of which can be linear, branched, or cyclic, and have 1 to 9 carbon atoms and up to 4 oxygen atoms when oxygen-containing or oxygen-substituted; and n is an integer from 1 to 12. Being oligomeric or polymeric in nature, these compounds exist as mixtures and are suitable for use as such. The perfluorinated repeating units may be arranged randomly, in blocks, or in an alternating sequence. For certain of these embodiments, the polyfluoropolyether segment comprises perfluorinated repeating units selected from the group consisting of —(C_(n)F_(2n)O)—, —(CF(Z)O)—, —(CF(Z)C_(n)F_(2n)O)—, —(C_(n)F_(2n)CF(Z)O)—, —(CF₂CF(Z)O)—, and combinations thereof. For certain of these embodiments, n is an integer from 1 to 12, 1 to 6, 1 to 4, or 1 to 3.

For certain embodiments, including any one of the above embodiments, R_(f) is monovalent, and z is 1. For certain of these embodiments, R_(f) is terminated with a group selected from the group consisting of C_(n)F_(2n+1)—, C_(n)F_(2n+1)O—, and X′C_(n)F_(2n)O— wherein X′ is a hydrogen or chlorine atom. For certain of these embodiments, the terminal group is C_(n)F_(2n+1)— or C_(n)F_(2n+1)O— wherein n is an integer from 1 to 6 or 1 to 3. For certain of these embodiments, the approximate average structure of R_(f) is C₃F₇O(CF(CF₃)CF₂O)_(p)CF(CF₃)— or CF₃O(C₂F₄O)_(p)CF₂— wherein the average value of p is 3 to 50.

For certain embodiments, including any one of the above embodiments except where R_(f) is monovalent, R_(f) is divalent, and z is 2. For certain of these embodiments, R_(f) is selected from the group consisting of —CF₂O(CF₂O)_(m)(C₂F₄O)_(p)CF₂—, —CF(CF₃)—(OCF₂CF(CF₃))_(p)O—R_(f)′—O(CF(CF₃)CF₂O)_(p)CF(CF₃)—, —CF₂O(C₂F₄O)_(p)CF₂—, and —(CF₂)₃O(C₄F₈O)_(p)(CF₂)₃—, and wherein R_(f)′ is a divalent, perfluoroalkylene group containing at least one carbon atom and optionally interrupted in chain by O or N, m is 1 to 50, and p is 3 to 40. For certain of these embodiments, R_(f)′ is (C_(n)F_(2n)), wherein n is 2 to 4. For certain of these embodiments, R_(f) is selected from the group consisting of —CF₂O(CF₂O)_(m)(C₂F₄O)_(p)CF₂—, —CF₂O(C₂F₄O)_(p)CF₂—, and —CF(CF₃)—(OCF₂CF(CF₃))_(p)O—(C_(n)F_(2n))—O(CF(CF₃)CF₂O)_(p)CF(CF₃)—, and wherein n is 2 to 4, and the average value of m+p or p+p or p is from about 4 to about 24.

The above described polyfluoropolyether silanes typically include a distribution of oligomers and/or polymers, so p and m may be non-integral. The above structures are approximate average structures where the approximate average is over this distribution. These distributions may also contain perfluoropolyethers with no silane groups or more than two silane groups. Typically, distributions containing less than about 10% by weight of compounds without silane groups can be used.

For certain embodiments, including any one of the above embodiments where the organic divalent linking group, Q′ is present, Q′ is a saturated or unsaturated hydrocarbon group including 1 to about 15 carbon atoms and optionally containing 1 to 4 heteroatoms and/or 1 to 4 functional groups. For certain of these embodiments, Q′ is a linear hydrocarbon containing 1 to about 10 carbon atoms, optionally containing 1 to 4 heteroatoms and/or 1 to 4 functional groups. For certain of these embodiments, Q′ contains one functional group. For certain of these embodiments, Q′ is preferably —C(O)N(R)(CH₂)₂—, —OC(O)N(R)(CH₂)₂—, —CH₂—O—(CH₂)₂—, or —CH₂—OC(O)N(R)—(CH₂)₂—, wherein R is hydrogen or C₁₋₄ alkyl.

For certain embodiments, including any one of the above embodiments where R is present, R is hydrogen.

For certain embodiments, including any one of the above embodiments where the hydrolyzable group Y or Y′ is present, each Y or Y′ is independently a group such as halogen, alkoxy, acyloxy, aryloxy, and polyalkyleneoxy. Alkoxy is —OR′, and acyloxy is —OC(O)R′, wherein each R′ is independently a lower alkyl group, optionally substituted by one or more halogen atoms. For certain embodiments, R′ is preferably C₁₋₆ alkyl and more preferably C₁₋₄ alkyl. Aryloxy is —OR″ wherein R″ is aryl optionally substituted by one or more substituents independently selected from halogen atoms and C₁₋₄ alkyl optionally substituted by one or more halogen atoms. For certain embodiments, R″ is preferably unsubstituted or substituted C₆₋₁₂ aryl and more preferably unsubstituted or substituted C₆₋₁₀ aryl. Polyalkyleneoxy is —O—(CHR⁴—CH₂O)_(q)—R³ wherein R³ is C₁₋₄ alkyl, R⁴ is hydrogen or methyl, with at least 70% of R⁴ being hydrogen, and q is 1 to 40, preferably 2 to 10.

For certain embodiments, including any one of the above embodiments, x is 0.

For certain embodiments, the number average molecular weight of the polyfluoropolyether silane is about 750 to about 6000, preferably about 800 to about 4000.

For certain embodiments, including any one of the above embodiments, particularly of Formula Ia, R_(f) is —CF₂O(CF₂O)_(m)(C₂F₄O)_(p)CF₂—, and Q′-C(R)₂—Si(Y′)_(3-x)(R^(1a))_(x) is C(O)NH(CH₂)₃Si(OR′)₃ wherein R′ is methyl or ethyl. For certain of these embodiments, m and p are each about 9 to 12.

The compounds of Formulas I and Ia described above can be synthesized using standard techniques. For example, commercially available or readily synthesized perfluoropolyether esters (or functional derivatives thereof) can be combined with a functionalized alkoxysilane, such as a 3-aminopropylalkoxysilane, according to U.S. Pat. No. 3,810,874 (Mitsch et al.). It will be understood that functional groups other than esters may be used with equal facility to incorporate silane groups into a perfluoropolyether.

Perfluoropolyether diesters, for example, may be prepared through direct fluorination of a hydrocarbon polyether diester. Direct fluorination involves contacting the hydrocarbon polyether diester with F₂ in a diluted form. The hydrogen atoms of the hydrocarbon polyether diester will be replaced with fluorine atoms, thereby generally resulting in the corresponding perfluoropolyether diester. Direct fluorination methods are disclosed in, for example, U.S. Pat. Nos. 5,578,278 (Fall et al.) and 5,658,962 (Moore et al.).

In another embodiment, the at least partially fluorinated composition comprising one or more a silane groups is a perfluoroalkyl silane of the following Formula II:

R² _(f)-Q²-SiX_(3-x)R² _(x)  II

wherein: R² _(f) is a perfluorinated group optionally containing one or more heteroatoms (for example, oxygen atoms); the connecting group Q² is a divalent alkylene group, arylene group, or mixture thereof, containing one or more heteroatoms (e.g., oxygen, nitrogen, or sulfur), or functional groups (e.g., carbonyl, amido, or sulfonamido), and containing about 2 to about 16 carbon atoms (preferably, about 3 to about 10 carbon atoms); R² is a lower alkyl group (e.g., a C₁₋₄ alkyl group, preferably, a methyl group); X is a halogen (for example, a chlorine atom), a lower alkoxy group (e.g., a C₁₋₄ alkoxy group, preferably, a methoxy or ethoxy group), or an acyloxy group (e.g., OC(O)R³, wherein R³ is a C₁₋₄ alkyl group); and x is 0 or 1. For certain embodiments, preferably x is 0. For certain of these embodiments, each X group is a lower alkoxy group. For certain of these embodiments, X is methoxy or ethoxy. Alternatively, the X groups include at least one acyloxy or halide group. For certain of these embodiments, each X is a halide, and for certain of these embodiments, each X is chloride.

For certain embodiments of Formula II, the perfluorinated group, R² _(f), can include linear, branched, or cyclic structures that may be saturated or unsaturated. For certain of these embodiments, R² _(f) is a perfluoroalkyl group (C_(n)F_(2n+1)), wherein n is about 3 to about 20, more preferably, about 3 to about 12, and most preferably, about 3 to about 8. The divalent Q² group can include linear, branched, or cyclic structures, that may be saturated or unsaturated. For certain of these embodiments, the divalent Q² group is a linear group containing heteroatoms or functional groups, for example, as described above.

Typically, suitable fluorinated silanes include a mixture of isomers (e.g., a mixture of compounds containing linear and branched perfluoroalkyl groups). Mixtures of perfluoroalkyl silanes exhibiting different values of n can also be used.

For certain embodiments, the perfluoroalkyl silane includes any one or any combination of the following: C₃F₇CH₂OCH₂CH₂CH₂Si(OCH₃)₃; C₇F₁₅CH₂OCH₂CH₂CH₂Si(OCH₃)₃; C₇F₁₅CH₂OCH₂CH₂CH₂Si(OCH₂CH₃)₃; C₇F₁₅CH₂OCH₂CH₂CH₂Si(CH₃)(OCH₃)₂; C₇F₁₅CH₂OCH₂CH₂CH₂SiCl₃; C₇F₁₅CH₂OCH₂CH₂CH₂Si(CH₃)Cl₂; C₇F₅CH₂OCH₂CH₂CH₂SiCl(OCH₃)₂; C₇F₁₅CH₂OCH₂CH₂CH₂SiCl₂(OC₂H₅); C₇F₁₅C(O)NHCH₂CH₂CH₂Si(OCH₃)₃; CF₃(CF₂CF(CF₃))₃CF₂C(O)NHCH₂CH₂CH₂Si(OCH₂CH₃)₃; C₈F₁₇SO₂N(CH₂CH₃)CH₂CH₂CH₂Si(OCH₃)₃; C₈F₁₇SO₂N(CH₂CH₃)CH₂CH₂CH₂Si(OCH₂CH₃)₃; C₄F₉SO₂N(CH₃)CH₂CH₂CH₂Si(OCH₃)₃; C₈F₁₇CH₂CH₂Si(OCH₃)₃; C₆F₁₃CH₂CH₂Si(OCH₂CH₃)₃; C₈F₁₇CH₂CH₂Si(OCH₂CH₃)₃; C₈F₁₇SO₂N(CH₂CH₃)CH₂CH₂CH₂SiCl₃; C₈F₁₇SO₂N(CH₃)CH₂CH₂CH₂Si(CH₃)Cl₂; and C₈F₁₇CH₂OCH₂CH₂CH₂Si(OAc)₃.

Methods of making perfluoroalkyl silanes of the Formula II are known. See, for example, U.S. Pat. No. 5,274,159 (Pellerite et al.).

In another embodiment, the at least partially fluorinated composition comprising at least one silane group is a fluorinated oligomeric silane of the Formula III:

A-M^(f) _(n)M^(h) _(m)M^(a) _(r)-G  III

wherein A represents hydrogen or the residue of an initiating species (i.e., an organic compound having a radical and that derives from the decomposition of a free radical initiator or that derives from a chain transfer agent);

M^(f) represents units derived from one or more fluorinated monomers;

M^(h) represents units derived from one or more non-fluorinated monomers;

M^(a) represents units having a silyl group represented by the formula SiY″₃

wherein each Y″ independently represents an alkyl group, an aryl group, or a hydrolyzable group as defined above; and

G is a monovalent organic group comprising the residue of a chain transfer agent, and having the formula: —S-Q″-SiY₃;

wherein Q″ is an organic divalent linking group as defined below, and

each Y is independently a hydrolyzable group according to any one of the above definitions of Y.

The total number of units represented by the sum of n, m, and r is generally at least 2 and preferably at least 3 so as to render the compound oligomeric. The value of n in the fluorinated oligomeric silane is between 1 and 100 and preferably between 1 and 20. The values of m and r are between 0 and 100 and preferably between 0 and 20. According to a preferred embodiment, the value of m is less than that of n and n+m+r is at least 2.

The fluorinated oligomeric silanes typically have an number average molecular weight between 400 and 100000, preferably between 600 and 20000, more preferably between 1000 and 10000. The fluorinated oligomeric silanes preferably contains at least mole % (based on total moles of units M^(f), M^(h), and M^(a)) of hydrolysable groups. When the units M^(h) and/or M^(a) are present the units M^(f), M^(h), and/or M^(a) may be randomly distributed.

It will further be appreciated by one skilled in the art that the preparation of fluorinated oligomeric silanes useful in the present invention results in a mixture of compounds and accordingly, general Formula III should be understood as representing a mixture of compounds whereby the indices n, m and r in Formula III represent the molar amounts of the corresponding unit in such mixture. Accordingly, it will be clear that n, m and r can be fractional values.

The units M^(f) _(n) of the fluorinated oligomeric silane are derived from fluorinated monomers, preferably fluorochemical acrylates and methacrylates.

Examples of fluorinated monomers for the preparation of the fluorinated oligomeric silane include those that can be represented by general formula:

R³ _(f)-Q″-E

wherein R³ _(f) represents a partially or fully fluorinated aliphatic group having at least 3 carbon atoms or a fluorinated polyether group, Q″ is a bond or an organic divalent linking group, and E represents an ethylenically unsaturated group. The ethylenically unsaturated group E can be fluorinated or non-fluorinated.

The partially or fully fluorinated aliphatic group, R³ _(f), in the fluorochemical monomer can be a fluorinated, preferably saturated, non-polar, monovalent aliphatic radical. It can be straight chain, branched chain, or cyclic or combinations thereof. It can contain heteroatoms such as oxygen, divalent or hexavalent sulfur, or nitrogen. R³ _(f) is preferably a fully-fluorinated radical, but hydrogen or chlorine atoms may be present if not more than one atom of either is present for every two carbon atoms. The R³ _(f) group has at least 2 and up to 18 carbon atoms, preferably 3 to 14, more preferably 4 to 10, especially 4. The terminal portion of the R³ _(f) group is a perfluorinated moiety, which will preferably contain at least 7 fluorine atoms, e.g., CF₃CF₂CF₂— and (CF₃)₂CF—. The preferred R³ _(f) groups are fully or substantially fluorinated and are preferably those perfluoroalkyl groups of the formula C_(n)F_(2n+1)— where n is 3 to 18, particularly 4 to 10. Compounds wherein the R³ _(f) group is a C₄F₉— are generally more environmentally friendly than compounds where the R³ _(f) group consists of a perfluorinated group with more carbon atoms.

The R³ _(f) group can also be a perfluoropolyether group, which can be include linear, branched, and/or cyclic structures, that may be saturated or unsaturated, and substituted with one or more oxygen atoms. For certain embodiments, R³ _(f) includes perfluorinated repeating units selected from the group consisting of —(C_(n)F_(2n))—, —(C_(n)F_(2n)O)—, —(CF(Z))—, —(CF(Z)O)—, —(CF(Z)C_(n)F_(2n)O)—, —(C_(n)F_(2n)CF(Z)O)—, —(CF₂CF(Z)O)—, and combinations thereof. For certain of these embodiments, Z is a perfluoroalkyl group, an oxygen-containing perfluoroalkyl group, a perfluoroalkoxy group, or an oxygen-substituted perfluoroalkoxy group, each of which can be linear, branched, or cyclic, and have 1 to 9 carbon atoms and up to 4 oxygen atoms when oxygen-containing or oxygen-substituted. For certain of these embodiments, R³ _(f) is terminated with a group selected from the group consisting of C_(n)F_(2n+1)—, C_(n)F_(2n+1)O—, and X′C_(n)F_(2n)O—, wherein X′ is a hydrogen or chlorine atom. For certain of these embodiments, the terminal group is C_(n)F_(2n+1)— or C_(n)F_(2n+1)O—. In these repeating units or terminal groups, n is an integer of 1 or more. For certain embodiments, n is an integer from 1 to 12, 1 to 6, or preferably 1 to 4. For certain of these embodiments, the approximate average structure of R³ _(f) is C₃F₇O(CF(CF₃)CF₂O)_(p)CF(CF₃)— or CF₃O(C₂F₄O)_(p)CF₂—, wherein the average value of p is 1 to about 50. As synthesized, these materials typically include a mixture of polymers. The approximate average structure is the approximate average of the mixture of polymers.

The linking group Q″ links the fluoroaliphatic or the fluorinated polyether group R³ _(f) to the free radical polymerizable group E, and is a generally non-fluorinated organic linking groups. The linking group can be a chemical bond, but preferably contains from 1 to about 20 carbon atoms and may optionally contain oxygen, nitrogen, or sulfur-containing groups or a combination thereof. The linking group is preferably free of functional groups that substantially interfere with free-radical oligomerization (e.g., polymerizable olefinic double bonds, thiols, and other such functionality known to those skilled in the art). Examples of suitable organic divalent linking groups, Q″, include, for example, —C(O)Q^(a)-R⁵-Q^(b)-C(O)—, —C(O)O—CH₂—CH(OH)—R⁵-Q^(a)-C(O)—, -L¹-Q^(a)-C(O)NH-L²-, —R⁵-Q^(a)-C(O)—, —C(O)Q^(a)-R⁵—, —R⁵—, —C(O)Q^(a)-R⁵-Q^(a)-, —S(O)₂NR—R⁵-Q^(a)-, —S(O)₂NR—R⁵—, and —S(O)₂NR—R⁵-Q^(a)-C(O)—, wherein Q^(a) and Q^(b) independently represent O or NR, R is hydrogen or C₁₋₄ alkyl, R⁵ represents a linear, cyclic or branched alkylene group that may be interrupted by one or more heteroatoms such as O or N, L¹ and L² each independently represent a non-fluorinated organic divalent linking group including an alkylene group, a carbonyl group, a carboxy amido alkylene group and/or a carboxy alkylene group. Preferred linking groups, Q″, include —S(O)₂N(R)—(CH₂)_(d)—OC(O)— and —(CH₂)_(d)—OC(O)—, where d is an integer from 1 to 20, preferably from 1 to 4.

Fluorochemical monomers R³ _(f)-Q″-E as described above and methods for the preparation thereof are known and disclosed, e.g., in U.S. Pat. No. 2,803,615 (Ahlbrecht et al.). Examples of such compounds include general classes of fluorochemical acrylates, methacrylates, vinyl ethers, and allyl compounds containing fluorinated sulfonamido groups, acrylates or methacrylates derived from fluorochemical telomer alcohols, acrylates or methacrylates derived from fluorochemical carboxylic acids, and perfluoroalkyl acrylates or methacrylates as disclosed in European Patent No. 0 526 976, published Jan. 15, 1997.

Perfluoropolyether acrylates or methacrylates are described in U.S. Pat. No. 4,085,137 (Mitsch et al.).

Preferred examples of fluorinated monomers include: CF₃(CF₂)₂CH₂OC(O)CH═CH₂, CF₃(CF₂)₂CH₂OC(O)C(CH₃)═CH₂, CF₃(CF₂)₃CH₂OC(O)C(CH₃)═CH₂, CF₃(CF₂)₃CH₂OC(O)CH═CH₂, CF₃(CF₂)₃S(O)₂N(R^(a))—(CH₂)₂—OC(O)CH═CH₂, CF₃(CF₂)₃S(O)₂N(R^(a))—(CH₂)₂—OC(O)C(CH₃)═CH₂, CF₃(CF₂)₃S(O)₂N(CH₃)—(CH₂)₂—OC(O)C(CH₃)═CH₂, CF₃(CF₂)₃S(O)₂N(CH₃)—(CH₂)₂—OC(O)CH═CH₂, CF₃CF₂(CF₂CF₂)₂₋₈(CH₂)₂OC(O)CH═CH₂, CF₃(CF₂)₇(CH₂)₂OC(O)CH═CH₂, CF₃(CF₂)₇(CH₂)₂OC(O)C(CH₃)═CH₂, CF₃(CF₂)₇S(O)₂N(R^(a))—(CH₂)₂—OC(O)CH═CH₂ CF₃ (CF₂)₇S(O)₂N(R^(a))—(CH₂)₂OC(O)C(CH₃)═CH₂, CF₃(CF₂)₇CH₂CH₂S(O)₂N(CH₃)—(CH₂)₂OC(O)C(CH₃)═CH₂ CF₃O(CF₂CF₂)_(u)CH₂OC(O)CH═CH₂, CF₃O(CF₂CF₂)_(u)CH₂OC(O)C(CH₃)═CH₂, C₃F₇O(CF(CF₃)CF₂O)_(u)CF(CF₃)CH₂OC(O)CH═CH₂, C₃F₇O(CF(CF₃)CF₂O)_(u)CF(CF₃)CH₂OC(O)C(CH₃)═CH₂, C₃F₇O(CF(CF₃)CF₂O)_(u)CF(CF₃)CONHCH2CH₂OC(O)C(CH₃)═CH₂, and C₃F₇O(CF(CF₃)CF₂O)_(u)CF(CF₃)CONHCH2CH₂OCONH—CH2CH2-OC(O)C(CH₃)═CH₂;

wherein R^(a) represents methyl, ethyl or n-butyl, and u is about 1 to 50.

The units M^(h) (when present) of the fluorinated oligomeric silane are generally derived from a non-fluorinated monomer, preferably a monomer consisting of a polymerizable group and a hydrocarbon moiety. Hydrocarbon group containing monomers are well known and generally commercially available. Examples of hydrocarbon containing monomers include those according to formula:

R^(h)-Q′″-E

wherein R^(h) is a hydrocarbon group, optionally containing one or more oxyalkylene groups or one or more reactive groups, such as hydroxy groups, amino groups, epoxy groups, and halogen atoms such as chlorine and bromine, Q′″ is a chemical bond or a divalent linking group as defined above for Q″, and E is an ethylenically unsaturated group as defined above. The hydrocarbon group is preferably selected from the group consisting of a linear, branched or cyclic alkyl group, an arylalkylene group, an alkylarylene group, and an aryl group. Preferred hydrocarbon groups contain from 4 to 30 carbon atoms.

Examples of non-fluorinated monomers from which the units M^(h) can be derived include general classes of ethylenic compounds capable of free-radical polymerization, such as allyl esters such as allyl acetate and allyl heptanoate; alkyl vinyl ethers or alkyl allyl ethers, such as cetyl vinyl ether, dodecyl vinyl ether, 2-chloroethyl vinyl ether, ethyl vinyl ether; anhydrides and esters of unsaturated acids such as acrylic acid, methacrylic acid, alpha-chloro acrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid; vinyl, allyl, methyl, butyl, isobutyl, hexyl, heptyl, 2-ethylhexyl, cyclohexyl, lauryl, stearyl, isobornyl or alkoxyethyl acrylates and methacrylates; alpha-beta unsaturated nitriles such as acrylonitrile, methacrylonitrile, 2-chloroacrylonitrile, 2-cyanoethyl acrylate, alkyl cyanoacrylates; allyl glycolate, acrylamide, methacrylamide, n-diisopropyl acrylamide, diacetoneacrylamide, N,N-diethylaminoethylmethacrylate, N-t-butylamino ethyl methacrylate; styrene and its derivatives such as vinyltoluene, alpha-methylstyrene, alpha-cyanomethyl styrene; lower olefinic hydrocarbons which can contain halogen such as ethylene, propylene, isobutene, 3-chloro-1-isobutene, butadiene, isoprene, chloro and dichlorobutadiene, 2,5-dimethyl-1,5-hexadiene, and allyl or vinyl halides such as vinyl and vinylidene chloride. Preferred non-fluorinated monomers include hydrocarbon group containing monomers such as those selected from octadecyl methacrylate, lauryl methacrylate, butyl acrylate, N-methylol-acrylamide, isobutyl methacrylate, ethylhexyl acrylate and ethylhexyl methacrylate; and vinylchloride and vinylidene chloride.

The fluorinated oligomeric silane useful in the invention generally further includes units M^(a) that have a silyl group with hydrolyzable groups at the terminus of the units derived from one or more non-fluorinated monomers as defined above. Examples of units M^(a) include those that correspond to the general formula:

E-Z—SiY″₃

wherein E is an ethylenically unsaturated group as defined above, Y″ is as defined above, and Z is a chemical bond or a divalent linking group containing 1 to 20 carbon atoms and optionally containing oxygen, nitrogen, or sulfur-containing groups or a combination thereof. Z is preferably free of functional groups that substantially interfere with free-radical oligomerization (e.g., polymerizable olefinic double bonds, thiols, and other such functional groups known to those skilled in the art). Examples of suitable linking groups Z include straight chain, branched chain, or cyclic alkylene, arylene, arylalkylene, oxyalkylene, carbonyloxyalkylene, oxycarboxyalkylene, carboxyamidoalkylene, oxycarbonylaminoalkylene, ureylenealkylene, and combinations thereof. For certain embodiments, Z is selected from the group consisting of alkylene, oxyalkylene, carbonyloxyalkylene, and the formula:

-Q³-T-C(O)NH-Q⁴-

wherein Q³ and Q⁴ are independently an organic divalent linking group selected from the group consisting of alkylene, arylene, oxyalkylene, carbonyloxyalkylene, oxycarboxyalkylene, carboxyamidoalkylene, oxycarbonylaminoalkylene, and ureylenealkylene; T is O or NR⁶ wherein R⁶ is hydrogen, C₁₋₄ alkyl, or aryl. For certain of these embodiments, Q⁴ is alkylene or arylene. Typical examples of such monomers include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, and alkoxysilane functionalized acrylates or methacrylates, such as trimethoxysilylpropyl methacrylate and the like.

The fluorinated oligomeric silane is conveniently prepared through a free radical polymerization of a fluorinated monomer with optionally a non-fluorinated monomer and/or a monomer containing the silyl group in the presence of a chain transfer agent. A free radical initiator is generally used to initiate the polymerization or oligomerization reaction. Commonly known free-radical initiators can be used and examples thereof include azo compounds, such as azobisisobutyronitrile (AIBN), azo-2-cyanovaleric acid and the like, hydroperoxides such as cumene, t-butyl and t-amyl hydroperoxide, dialkyl peroxides such as di-t-butyl and dicumylperoxide, peroxyesters such as t-butylperbenzoate and di-t-butylperoxy phthalate, diacylperoxides such as benzoyl peroxide and lauroyl peroxide.

The oligomerization reaction can be carried out in any solvent suitable for organic free-radical reactions. The reactants can be present in the solvent at any suitable concentration (e.g., from about 5 percent to about 90 percent by weight based on the total weight of the reaction mixture). Examples of suitable solvents include aliphatic and alicyclic hydrocarbons (e.g., hexane, heptane, cyclohexane), aromatic solvents (e.g., benzene, toluene, xylene), ethers (e.g., diethylether, glyme, diglyme, diisopropyl ether), esters (e.g., ethyl acetate, butyl acetate), alcohols (e.g., ethanol, isopropyl alcohol), ketones (e.g., acetone, methylethyl ketone, methyl isobutyl ketone), sulfoxides (e.g., dimethyl sulfoxide), amides (e.g., N,N-dimethylformamide, N,N-dimethylacetamide), halogenated solvents such as methylchloroform, 1,1,2-trichloro-1,2,2-trifluoroethane, trichloroethylene, α,α,α-trifluorotoluene, and the like, and mixtures thereof.

The oligomerization reaction can be carried out at any temperature suitable for conducting an organic free-radical reaction. Particular temperature and solvents for use can be easily selected by those skilled in the art based on considerations such as the solubility of reagents, the temperature required for the use of a particular initiator, molecular weight desired and the like. While it is not practical to enumerate a particular temperature suitable for all initiators and all solvents, generally suitable temperatures are between about 30° C. and about 200° C., preferably between 50° C. and 100° C.

The fluorinated oligomeric silane is typically prepared in the presence of a chain transfer agent. Suitable chain transfer agents may include a hydroxy-, amino-, mercapto or halogen group. The chain transfer agent may include two or more of such hydroxy, amino-, mercapto or halogen groups. Typical chain transfer agents useful in the preparation of the fluorinated oligomeric silane include those selected from 2-mercaptoethanol, 3-mercapto-2-butanol, 3-mercapto-2-propanol, 3-mercapto-1-propanol, 3-mercapto-1,2-propanediol, 2-mercaptoethylamine, di(2-mercaptoethyl)sulfide, octylmercaptane, and dodecylmercaptane.

In a preferred embodiment, a chain transfer agent containing a silyl group having hydrolyzable groups is used in the oligomerization to produce the fluorinated oligomeric silane. Such chain transfer agents are of the following formula:

HS-Q⁵-SiY₃

wherein Q⁵ represents an organic divalent linking group such as for example a straight chain, branched chain or cyclic alkylene, arylene or arylalkylene; and each Y is independently a hydrolyzable group as defined above. Q⁵ is preferably C₁₋₂₀ alkylene.

Alternatively, a functionalized chain transfer agent or functionalized co-monomer can be used in the oligomerization. The functional group introduced by the functionalized chain transfer agent or functionalized co-monomer can then be reacted with a silyl group containing reagent subsequent to the oligomerization to introduce a silyl group having hydrolyzable groups.

A single chain transfer agent or a mixture of different chain transfer agents may be used. For certain embodiments, 2-mercaptoethanol, octylmercaptane, and 3-mercaptopropyltrimethoxysilane are preferred chain transfer agents. A chain transfer agent is typically present in an amount sufficient to control the number of polymerized monomer units in the oligomer and to obtain the desired molecular weight of the oligomeric fluorochemical silane.

The fluorinated oligomeric silane can be prepared by oligomerizing a fluorinated monomer and optional non-fluorinated monomer with a monomer E-Z—SiY″₃, wherein at least one Y″ represents a hydrolysable group, in the presence of a chain transfer agent which may optionally also contain a silyl group such as, for example, HS-Q⁵-SiY₃.

As a variation to the above method the oligomerization may be carried out without the use of the silyl group containing monomer but with a chain transfer agent containing the silyl group.

In another embodiment, the at least partially fluorinated composition comprising at least one silane group is a swallow-tail silane of the Formula IV:

R⁴ _(f)S(O)₂—N(R⁷)—(C_(n)H_(2n))—CH(Z¹)—(C_(m)H_(2m))—N(R⁸)—S(O)₂R⁴ _(f)  IV

wherein each R⁴ _(f) is independently C_(p)F_(2p+1), wherein p is 1 to 8; R⁷ is C₁₋₄ alkyl or aryl; m and n are both integers from 1 to 20; Z¹ is hydrogen or a group of the formula —(CC_(m′)H_(2m′)—X) ¹-Q⁵-Si(Y)₃ wherein m′ is 0 to 4, X¹ is O, S, or NH, Q⁵ is —C(O)NH—(CH₂)_(n′)— or —(CH₂)_(n′)—, n′ is an integer of 1 to 20, and Y is a hydrolysable group; and R⁸ is R⁷ or a group of the formula —(CH₂)_(n′)—Si(Y)₃, with the proviso that when Z¹ is hydrogen, then R⁸ is a group of the formula —(CH₂)_(n′)—Si(Y)₃.

Each R⁴ _(f) may be the same or different, and each contains 1-8 carbon atoms, preferably 2-5 carbon atoms, more preferably 4 carbon atoms.

For certain embodiments, including any one of the above embodiments of Formula IV, m is an integer from 1 to 6, and n is an integer from 1 to 6.

For certain embodiments, including any one of the above embodiments of Formula IV, R⁷ is C₁₋₄ alkyl. For certain of these embodiments, C₁₋₄ alkyl is methyl or ethyl.

For certain embodiments, including any one of the above embodiments of Formula IV, R⁸ is C₁₋₄ alkyl. For certain of these embodiments, C₁₋₄ alkyl is methyl or ethyl.

For certain embodiments, including any one of the above embodiments of Formula N except where R⁷ is C₁₋₄ alkyl, R⁷ is aryl.

For certain embodiments, including any one of the above embodiments of Formula IV except where R⁸ is C₁₋₄ alkyl, R⁸ is aryl.

For certain embodiments where R⁷ and/or R⁸ is aryl, aryl is phenyl which is unsubstituted or substituted by one or up to five substituents independently selected from the group consisting of C₁₋₄ alkyl, C₁₋₄ alkoxy, halogen (e.g. fluoro, chloro, bromo, and/or iodo groups), hydroxy, amino, and nitro. When substituents are present, halogen and C₁₋₄ alkyl substituents are preferred.

For certain embodiments, including any one of the above embodiments of Formula N, n′ is an integer from 1 to 10, and in one embodiment n′ is 3.

For certain embodiments, including any one of the above embodiments of Formula IV, Y is defined as in any one of the above definitions of Y. For certain of these embodiments, Y is —OC₁₋₄ alkyl, —OC(O)CH₃, or Cl.

For certain embodiments, swallow-tail silanes of the Formula IV include, but are not limited to [C₄F₉S(O)₂N(CH₃)CH₂]₂CHOCH₂CH₂CH₂Si(OCH₃)₃, [C₄F₉S(O)₂N(CH₃)CH₂]₂CHOC(O)NHCH₂CH₂CH₂Si(OCH₃)₃, and C₄F₉S(O)₂N(CH₃)CH₂CH₂CH₂N(S(O)₂C₄F₉)CH₂CH₂CH₂Si(OCH₃)₃.

The swallow-tail silane of the Formula N may be prepared by known methods. For example, [C₄F₉S(O)₂N(CH₃)CH₂]₂CHOH may be made by reacting two moles of C₄F₉S(O)₂NHCH₃ with either 1,3-dichloro-2-propanol or epichlorohydrin in the presence of a base. [C₄F₉S(O)₂N(CH₃)CH₂]₂CHOCH₂CH₂CH₂Si(OCH₃)₃ can be made from [C₄F₉S(O)₂N(CH₃)CH₂]₂CHOH by alkylation with ClCH₂CH₂CH₂Si(OCH₃)₃ or by alkylation with allyl chloride, followed by hydrosilation with HSiCl₃ and methanolysis. Reaction of [C₄F₉S(O)₂N(CH₃)CH₂]₂CHOH with OCNCH₂CH₂CH₂Si(OCH₃)₃ yields [C₄F₉S(O)₂N(CH₃)CH₂]₂CHOC(O)NHCH₂CH₂CH₂Si(OCH₃)₃.

In another embodiment, the at least partially fluorinated composition comprising at least one silane group is a hexafluoropropyleneoxide (HFPO) quat silane. For example, quat silanes with general Formula V or VI can be used:

wherein b and c is each independently an integer of 1 to 3; R_(f) is a perfluorinated ether group; A is a linking group having the formula —C_(d)H_(2d)ZC_(g)H_(2g)—, wherein d and g are independently integers from 0 to 10 and Z is selected from the group consisting of a covalent bond, a carbonyl group, a sulfonyl group, a carboxamido group, a sulfonamido group, an iminocarbonyl group, an iminosulfonyl group, an oxycarbonyl group, a urea group, a urethane group, a carbonate group, and a carbonyloxy group; Y is a bridging group having 1 to 10 carbon atoms, a valency of 2 to 6, and comprising at least one of an alkylene group or an arylene group; Q is a connecting group having 1 to 10 carbon atoms, a valency of 2 to 6, and comprising at least one of an alkylene group or an arylene group; R¹ and R² are independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and an aralkyl group; each R³ is independently selected from the group consisting of hydroxy groups, alkoxy groups, acyl groups, acyloxy groups, halo groups, and polyether groups; and X⁻ is a counter ion selected from the group consisting of inorganic anions organic anions, and combinations thereof.

wherein R_(f) has the structure —CF(CF₃)(OCF₂CF(CF₃))_(m)OCF₂CF₂CF₂CF₂O(CF(CF₃)CF₂O)_(n)CF(CF₃)—, wherein m is an integer of 1 to 12 and n is an integer of 2 to 10; c is an integer from about 1 to about 3; A is a linking group having the formula —C_(d)H_(2d)ZC_(g)H_(2g)—, wherein d and g are independently integers from about 0 to about 10 and Z is selected from the group consisting of a covalent bond, a carbonyl group, a sulfonyl group, a carboxamido group, a sulfonamido group, an iminocarbonyl group, an iminosulfonyl group, an oxycarbonyl group, a urea group, a urethane group, a carbonate group, and a carbonyloxy group; Y is a bridging group comprising an alkylene group having about 1 to about 6 carbon atoms; Q is a connecting group comprising an alkylene group having about 1 to about 6 carbon atoms; R¹ and R² are independently alkyl groups having about 1 to about 4 carbon atoms; each R³ is independently selected from the group consisting of hydroxy groups, methoxy groups, ethoxy groups, acetoxy groups, chloro groups, and polyether groups; and X⁻ is a counter ion selected from the group consisting of a halide, sulfate, phosphate, an alkyl sulfonate, an aryl sulfonate, an alkyl phosphonate, an aryl phosphonate, a fluorinated alkyl sulfonate, a fluorinated aryl sulfonate, a fluorinated alkyl sulfonimide, a fluorinated alkyl methide, and combinations thereof.

In other embodiments, particularly when the tie layer comprises diamond-like glass, the at least partially fluorinated composition comprising at least one silane group comprises a composition comprising:

(a) a first polyfluoropolyether silane of the Formula VIIIa:

CF₃CF₂CF₂O(CF(CF₃)CF₂O)_(p)CF(CF₃)—C(O)NH(CH₂)₃Si(Y)₃  VIIa

-   -   wherein each Y is independently a hydrolyzable group and wherein         p is 3 to 50; and

(b) a second polyfluoropolyether silane of the Formula IIXa:

(Y)₃Si(CH₂)₃NHC(O)—CF₂O(CF₂O)_(m)(C₂F₄O)_(q)CF₂—C(O)NH(CH₂)₃Si(Y′)₃  IIXa

-   -   wherein each Y′ is independently a hydrolyzable group and         wherein m is 1 to 50 and q is 3 to 40.         Hydrolyzable groups, Y and Y′ of Formula VIIa and IIXa,         respectively may be the same or different (within a compound of         a Formula and between compounds of Formula VIIIa and IIXa).         Favorably such groups are capable of hydrolyzing, for example,         in the presence of water, optionally under acidic or basic         conditions, producing groups capable of undergoing a         condensation reaction, for example silanol groups. For example,         methoxy and ethoxy groups form essentially immediately “in situ”         (e.g. in the presence of water, optionally under acidic or basic         conditions) hydroxy groups, thus producing silanol groups.         Desirably, each Y of Formula VIIa and each Y′ of Formula IIXa         are independently groups selected from the group consisting of         hydrogen, halogen, alkoxy, acyloxy, aryloxy, and         polyalkyleneoxy, more desirably each Y of Formula VIIIa and each         Y′ of Formula IIXa are independently groups selected from the         group consisting of alkoxy, acyloxy, aryloxy, and         polyalkyleneoxy, even more desirably each Y of Formula VIIa and         each Y′ of Formula IIXa are independently groups selected from         the group consisting of alkoxy, acyloxy and aryloxy, and most         desirably each Y of Formula VIIa and each Y′ of Formula IIXa are         independently alkoxy groups, in particular lower (C1-C4) alkoxy         groups, more particularly methoxy and/or ethoxy groups.

Similarly, the at least partially fluorinated composition comprising at least one silane group can comprises a composition comprising:

(a) a first polyfluoropolyether silane entity of the Formula VIIb:

CF₃CF₂CF₂O(CF(CF₃)CF₂O)_(p)CF(CF₃)—C(O)NH(CH₂)₃Si(O—)₃  VIIb

-   -   wherein p is 3 to 50; and

(b) a second polyfluoropolyether silane entity of the Formula IIXb:

(—O)₃Si(CH₂)₃NHC(O)—CF₂O(CF₂O)_(m)(C₂F₄O)_(g)CF₂—C(O)NH(CH₂)₃Si(O—)₃  IIXb

-   -   wherein m is 1 to 50 and q is 3 to 40.

Compounds in accordance with Formula VIIIa and IIXa as described above can be synthesized using standard techniques. For example, commercially available or readily synthesized polyfluoropolyether esters (or functional derivatives thereof) can be combined with 3-aminopropylalkoxysilane, and methods described in U.S. Pat. Nos. 3,250,808 (Moore), 3,646,085 (Barlett), 3,810,874 (Mitsch et al.) and CA Patent No. 725747 (Moore) can be used to prepare compounds in accordance with Formula VIIIa and IIXa.

For certain embodiments, the p in Formula VIIIa or VIIb is from about 3 to about 20, in particular from about 4 to about 10. For certain embodiments, for Formula IIXa or IIXb m+q or q is from about 4 to about 24, in particular m and q are each about 9 to about 12. For certain embodiments, the weight average molecular weight of the polyfluoropolyether segment of the first polyfluoropolyether silane of the Formula VIIIa or VIIb is about 900 or higher, in particular about 1000 or higher. For certain embodiments, the weight average molecular weight of the polyfluoropolyether segment of the second polyfluoropolyether silane of the Formula IIXa or II b is about 1000 or higher, in particular about 1800 or higher. Generally, the weight average molecular weight of the polyfluoropolyether segment of the second polyfluoropolyether silane of the Formula IIXa is desirably about 6000 at most, in particular about 4000 at most and/or the weight average molecular weight of the polyfluoropolyether segment of the first polyfluoropolyether silane of the Formula VIIIa is about 4000 at most, in particular about 2500 at most.

Polyfluoropolyether silanes typically include a distribution of oligomers and/or polymers. Desirably, the amount of polyfluoropolyether silane (in such a distribution) having a polyfluoropolyether segment having a weight average molecular weight less than 750 is not more than 10% by weight (more desirably not more than 5% by weight, and even more desirably not more 1% by weight and most desirably 0%) of total amount of polyfluoropolyether silane in said distribution.

The above structures are approximate average structures where p and m and q designate the number of randomly distributed perfluorinated repeating units. Further, as mentioned above polyfluoropolyether silanes described herein typically include a distribution of oligomers and/or polymers, so p and/or m and/or q may be non-integral and where the number is the approximate average is over this distribution.

Certain favorable embodiments of the composition comprise first and second polyfluoropolyether silane entities as described above desirably having a weight percent ratio of the first to second polyfluoropolyether silane entity (first polyfluoropolyether silane entity:second fluoropolyether silane entity) equal to or greater than 10:90, in particular equal to or greater than 20:80, more particularly equal to or greater than 30:70, most particularly equal to or greater than 40:60. Other desirable embodiments of the composition comprise first and second polyfluoropolyether silane entities as described above having the weight percent ratio of the first to second polyfluoropolyether silane (first polyfluoropolyether silane:second polyfluoropolyether silane) equal to or less than 99:1, in particular equal to or less than 97:3, most particularly equal to or less than 95:5.

For certain embodiments, including any one of the above embodiments, the at least partially fluorinated composition comprising at least one silane group further includes an organic solvent.

For certain embodiments, including any one of the above embodiments wherein the at least partially fluorinated composition comprising at least one silane group is a polyfluoropolyether silane, the polyfluoropolyether silane is applied as a composition comprising the polyfluoropolyether silane and an organic solvent.

The organic solvent or blend of organic solvents used must be capable of dissolving at least about 0.01 percent by weight of one or more silanes of the Formulas I through IV. For certain embodiments, it is desirable that the solvent or mixture of solvents have a solubility for water of at least about 0.1 percent by weight, and for certain of these embodiments, a solubility for acid of at least about 0.01 percent by weight.

Suitable organic solvents, or mixtures of solvents can be selected from aliphatic alcohols, such as methanol, ethanol, and isopropanol; ketones such as acetone and methyl ethyl ketone; esters Such as ethyl acetate and methyl formate; ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether and dipropyleneglycol monomethylether (DPM); hydrocarbons solvents such as alkanes, for example, heptane, decane, and paraffinic solvents; fluorinated hydrocarbons such as perfluorohexane and perfluorooctane; partially fluorinated hydrocarbons, such as pentafluorobutane; hydrofluoroethers such as methyl perfluorobutyl ether and ethyl perfluorobutyl ether.

For certain embodiments, including any one of the above embodiments, the organic solvent is a fluorinated solvent, which includes fluorinated hydrocarbons, partially fluorinated hydrocarbons, and hydrofluoroethers. For certain of these embodiments, the fluorinated solvent is a hydrofluoroether. For certain of these embodiments, the hydrofluoroether is methyl perfluorobutyl ether.

For certain embodiments, including any one of the above embodiments except where the organic solvent is a fluorinated solvent, the organic solvent is a lower alcohol. For certain of these embodiments, the lower alcohol is selected from the group consisting of methanol, ethanol, isopropanol, and mixtures thereof. For certain of these embodiments, the lower alcohol is ethanol.

For certain embodiments, including any one of the above embodiments where the organic solvent is a lower alcohol, the at least partially fluorinated composition comprising at least one silane group further comprises an acid. For certain of these embodiments, the acid is selected from the group consisting of acetic acid, citric acid, formic acid, triflic acid, perfluorobutyric acid, sulfuric acid, and hydrochloric acid. For certain of these embodiments, the acid is hydrochloric acid.

The at least partially fluorinated composition comprising at least one silane group, including any one of the above embodiments, can be applied to at least a portion of the surface of the layer comprising the silicon, oxygen, and hydrogen using a variety of coating methods. Such methods include but are not limited to spraying, dipping, rolling, brushing, spreading, flow coating, and vapor deposition.

Typically the at least partially fluorinated composition comprising at least one silane group is a monolayer that is from about 0.001 to about 1 micron thick; preferably from about 0.001 to about 0.10 microns thick.

For certain embodiments, including any one of the above embodiments, the at least partially fluorinated composition comprising at least one silane group, in any one of its above described embodiments, is applied by dipping at least a portion of the substrate upon which the layer comprising the silicon, oxygen, and hydrogen has been formed in the at least partially fluorinated composition comprising at least one silane group.

Alternatively, for certain embodiments, including any one of the above embodiments, the at least partially fluorinated composition comprising at least one silane group, in any one of its above described embodiments, is applied by spraying at least a portion of the substrate upon which the layer comprising the silicon, oxygen, and hydrogen has been formed with the at least partially fluorinated composition comprising at least one silane group.

For certain embodiments, including any one of the above embodiments except where the at least partially fluorinated composition comprising at least one silane group, is applied by other means, the at least partially fluorinated composition comprising at least one silane group, in any one of its above described embodiments, is applied by chemical vapor deposition to at least a portion of the substrate upon which the layer comprising the silicon, oxygen, and hydrogen has been formed. For certain of these embodiments, the at least partially fluorinated composition comprising at least one silane group is a polyfluoropolyether silane.

The conditions under which the at least partially fluorinated composition comprising at least one silane group, for example, the polyfluoropolyether silane is vaporized during chemical vapor deposition may vary according to the structure and molecular weight of the polyfluoropolyether silane. For certain embodiments, the vaporizing may take place at pressures less than about 1.3 Pa (about 0.01 torr), at pressures less than about 0.013 Pa (about 10⁻⁴ torr) or even about 0.0013 Pa to about 0.00013 Pa (about 10⁻⁵ torr to about 10⁻⁶ torr). For certain of these embodiments, the vaporizing may take place at temperatures of at least about 80° C., at least about 100° C., at least about 200° C., or at least about 300° C. Vaporizing may include imparting energy by, for example conductive heating, convective heating, microwave radiation heating, and the like.

The chemical vapor deposition method may reduce opportunities for contamination of the surface of the substrate through additional handling and exposure to the environment, leading to correspondingly lower yield losses. Furthermore, as the layer comprising silicon, oxygen, and hydrogen is formed by plasma deposition, it can be more efficient to apply the at least partially fluorinated composition comprising at least one silane group, for example, the polyfluoropolyether silanes in the same chamber or a connected vacuum chamber. Additionally, the polyfluoropolyether silane coatings applied by chemical vapor deposition may not need acid conditions and/or additional heating for curing. Useful vacuum chambers and equipment are known in the art. Examples include the Plasmatherm Model 3032 (available from Plasmatherm, Kresson, N.J.) and the 900 DLS (available from Satis Vacuum of America, Grove Port, Ohio).

In one embodiment, applying the polyfluoropolyether silane by chemical vapor deposition comprises placing the polyfluoropolyether silane and the substrate, having the layer comprising silicon, oxygen, and hydrogen on at least a portion of the surface of the substrate, into a chamber, decreasing the pressure in the chamber, and heating the polyfluoropolyether silane. The polyfluoropolyether silane is typically maintained in a crucible, but in some embodiments, the silane is imbibed in a porous matrix, such as a ceramic pellet, and the pellet heated in the vacuum chamber.

The at least partially fluorinated composition comprising at least one silane group, including any one of the above embodiments of Formulas I, II, III, and/or IV, undergoes reaction with the layer comprising the silicon, oxygen, and hydrogen on the substrate surface, for example, with —SiOH groups, to form a durable coating, through the formation of covalent bonds, including bonds in Si—O—Si groups. For the preparation of a durable coating, sufficient water should be present to cause hydrolysis of the hydrolyzable groups described above so that condensation to form Si—O—Si groups takes place, and thereby curing takes place. The water can be present either in the coating composition or adsorbed to the substrate surface, for example. Typically, sufficient water is present for the preparation of a durable coating if the coating method is carried out at room temperature in an atmosphere containing water, for example, an atmosphere having a relative humidity of about 30% to about 50%.

A substrate to be coated can typically be contacted with the coating composition at room temperature (typically, about 15° C. to about 30° C., or about 20° C. to about 25° C.). Alternatively, the coating composition can be applied to substrates which are preheated at a temperature of, for example, between 60° C. and 150° C. Following application of the at least partially fluorinated composition comprising at least one silane group, the treated substrate can be dried and the resulting coating cured at ambient temperature, e.g., about 15° C. to about 30° C., or elevated temperature (e.g., at about 40° C. to about 300° C.) and for a time sufficient for the curing to take place.

For certain embodiments, including any one of the above embodiments, the method of the invention further comprises the step of subjecting the substrate to an elevated temperature after applying the at least partially fluorinated composition comprising at least one silane group.

For certain embodiments, including any one of the above embodiments where the at least partially fluorinated composition comprising at least one silane group is a polyfluoropolyether silane, the method of the invention comprises the step of subjecting the substrate to an elevated temperature after applying the polyfluoropolyether silane.

For certain embodiments, including any one of the above embodiments where the at least partially fluorinated composition comprising at least one silane group further comprises an acid, except where an elevated temperature is used, the method of the invention further comprises the step of allowing the substrate to dry at a temperature of about 15° C. to about 30° C. after applying the composition.

In a preferred embodiment of the method of the invention for making a coated metal article, the three steps of forming a hardcoat layer by physical vapor deposition, forming a tie layer by plasma deposition, applying an at least partially fluorinated composition comprising at least one silane group by evaporation and condensation are performed within a single deposition chamber. This embodiment of the method of the invention is referred to herein as the “triple hybrid” method.

In a most preferred embodiment of the triple hybrid method of the invention, the hardcoat layer is formed using cathodic arc deposition, the tie layer is formed using ion-assisted plasma deposition, and the at least partially fluorinated composition is applied by thermal evaporation and condensation of the composition.

The triple hybrid method can be carried out in a deposition apparatus with a common element for plasma creation and ion acceleration. In one illustrative embodiment, the apparatus is a stainless steel vacuum chamber, cylindrical in shape, which is approximately two feet in diameter and two feet tall. The chamber is pumped by a Varian diffusion pump, which is backed by a rotary vane mechanical pump. The base pressure of the chamber is about 1×10⁻⁶ Torr. Coated metal articles of the invention can be mounted to a substrate platen, which is rotated at a speed of about 5 rpm. The substrate platen is electrically isolated from the chamber and connected to a 5 kilowatt RF power supply through an impedance matching transformer. The frequency of the applied RF power is 40 kHz. A cathodic arc evaporation source is installed on one of the flanges to the vacuum chamber. It comprises a 2 inch diameter metal cathode, which is cooled by water directly in contact with the back of the cathode. The cathode is connected to the negative terminal of a 200 ampere DC power supply. The positive terminal of the power supply is grounded to the chamber wall. A mechanical igniter is utilized to initiate the arc on the cathode. For plasma deposition of the tie layer, tetramethylsilane and oxygen, for example, can be metered into the chamber through mass flow controllers at prescribed flow rates. The plasma is initiated by the 40 kHz power supply. Evaporation of the at least partially fluorinated composition can be achieved, for example, by soaking a graphite cloth with a prescribed amount of fluorocompound and passing AC voltage to the graphite cloth to heat it in order to flash vaporized the fluorocompound. Current to the cloth is controlled by using a variable autotransformer (Variac).

After pumping the system to its base pressure, argon gas, for example, is introduced into the chamber at a prescribed flow rate and the RF power to the substrate platen is applied to create a plasma around the platen comprising the metal article. The metal article is cleaned in the argon plasma for prescribed amount of time, followed by treatment in, for example, a nitrogen plasma. Nitrogen gas at a prescribed flow rate is fed into the system and the argon is turned off while maintaining the plasma through the transition. After treating the metal article in a nitrogen plasma, the cathodic arc is initiated by activating the mechanical igniter. The nitrogen flow is maintained at the prescribed flow rate and the arc is maintained at the prescribed current in the DC power supply driving the cathodic arc discharge. After depositing the PVD coating by the cathodic arc method, the DC power is shut off and plasma priming is performed, for example, with oxygen and tetramethylsilane gases for a prescribed amount of time. Upon completion of the plasma priming resulting in the deposition of a silicon-containing tie layer, the plasma is shut off and power is applied to the graphite heating cloth to evaporate the fluorocompound onto the metal article.

EXAMPLES

Objects and advantages of this invention are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention.

Preparation of “HFPO-Silane”

“HFPO” refers to the end group —F(CF(CF₃)CF₂O)_(a)CF(CF₃)— of the methyl ester F(CF(CF₃)CF₂O)_(a)CF(CF₃)C(O)OCH₃, wherein a averages from 4-20, which can be prepared according to the method reported in U.S. Pat. No. 3,250,808, with purification by fractional distillation.

HFPO-Silane, HFPO-CONHCH₂CH₂Si(OCH₃)₃, was prepared as follows. A 100 mL 3 necked round bottom flask equipped with magnetic stir bar, N₂ inlet and reflux condenser was charged with HFPOCOOCH₃ (20 g, 0.01579 moles) and NH₂CH₂CH₂CH₂—Si(OCH₃)₃ (2.82 g, 0.01579 moles) under N₂ atmosphere. The reaction mixture was heated at 75° C. for 12 hours. The reaction was monitored by IR and after the disappearance of the ester peak, clear viscous oil was kept at high vacuum for another 8 hours and used as such as described below.

General Procedure

The following general triple hybrid method was carried out in a deposition apparatus, as described above, with a common element for plasma creation and ion acceleration:

-   -   Metal articles were mounted onto the substrate platen     -   Vacuum chamber was closed     -   Vacuum chamber was pumped to base pressure     -   Argon gas was introduced into the chamber     -   RF power was applied to the substrate platen     -   Metal articles were plasma cleaned in argon plasma     -   Nitrogen gas was introduced into the chamber     -   Argon gas was disabled     -   Metal articles were plasma treated in nitrogen plasma     -   Cathodic arc discharge was ignited     -   Nitrogen flow rate and substrate power were adjusted     -   Cathodic arc thin film was deposited onto metal articles     -   Cathodic arc discharge was disabled     -   Oxygen gas was introduced into the chamber     -   Nitrogen gas was disabled     -   Metal articles were plasma treated in oxygen plasma     -   Tetramethylsilane (TMS) gas was introduced into the chamber     -   Metal articles were plasma treated in oxygen plus TMS gas     -   TMS gas was disabled     -   Metal articles were plasma treated in oxygen gas     -   Oxygen gas was disabled     -   AC power was applied to the graphite heating cloth     -   Fluorocompound was evaporated and condensed onto metal articles     -   Power to the graphite cloth was disabled     -   The chamber was vented and metal articles were dismounted

Coating Evaluation: Tape Snap and Adhesive Removal Test

A tape snap/adhesive removal test was performed by applying and “snapping off” (quickly removing) 3M Catalog number 165 storage tape having an aggressive acrylic pressure sensitive adhesive ten times from the surface of metal articles. Then 3M catalog number 007A rubber-based pressure sensitive transfer adhesive was applied to the surface and rubbed off the surface with a finger. A relative rating scale was used for the tape snap/adhesive removal test as indicated in the table below.

Rating Description 1 Very easy to remove 007A adhesive 2 Easy to remove 007A adhesive 3 Less easy to remove 007A adhesive 4 Difficult to remove 007A adhesive 5 Very difficult to remove 007A adhesive

Example 1 Scissor Blades with Titanium Nitride, Diamond Like Glass (DLG), and Hexafluoropropyleneoxide (HFPO)-Silane Triple Layers

Stainless steel scissor blades were coated by the method of this invention according to the General Procedure above. The process parameters were as follows:

Flow Rate Pressure Rf Power DC Current Time Step Gas (sccm) (mTorr) (watts) (amps) (min) 1 O2 380 39 1000 — 30 2 Ar 300 39 1000 — 30 3 N2 400 49 500 — 5 4 N2 350 35 500 100 30 5 O2 380 38 500 — 3 6 TMS/O2 150/380 100 500 — 0.17 7 O2 380 55 500 — 3

During step 4 above, the cathodic arc source was enabled with a titanium cathode to evaporate titanium vapor which reacts with the nitrogen gas to deposit a titanium nitride hardcoat. The arc current was maintained at 100 amperes, resulting in a voltage of between 20 and 30 volts.

After completing the seven steps above, oxygen gas was disabled and chamber pressure reduced to less than 5×10-5 Torr. After this, electrical power to the graphite cleaning cloth was enabled and the HPPO-silane was evaporated onto the scissor blades. The Variac heating was set to 20% of full scale (approximately 20 volts) and the heating was left on for 60 seconds. Immediately following the HFPO deposition step, the chamber was vented to atmosphere and the scissor blades taken out of the system. The resulting blades had a gold color, characteristic of the titanium nitride thin films, and had good release characteristics as evidenced by the dewetting of Super Sharpie™ marker ink.

Example 2 Scissor Blades with Titanium Nitride, DLG, and (HFPO)-Silane or Perfluoropolyether Silane Triple Layers

A series of runs were completed on stainless steel scissor blades in essentially the same fashion as in Example 1 with either Novec™ EGC-1720, perfluoropolyether silane solubilized at 0.1 wt. % in hydrofluoroether solvent, available from 3M Company (“perfluoropolyether silane”) or HFPO-silane as indicated in Table 1. The scissor blades were then evaluated using the tape snap and adhesive removal test described above. The evaluation results are included in Table 1.

TABLE 1 Tape Hard Snap/Adhesive Coating Fluorochemical Removal Material Plasma Prime Coating Test Rating TiN Oxidized Silane DLG Perfluoropolyether 1 silane TiN Oxidized Silane DLG Perfluoropolyether 1 silane TiN Oxidized Silane DLG HFPO Silane 1 TiN Oxidized Silane DLG HFPO Silane 1 TiN Oxidized Silane DLG HFPO Silane 1

Example 3 Scissor Blades with Titanium Aluminum Nitride, DLG, and Perfluoropolyether Silane Triple Layers

Stainless steel scissor blades with a 0.6 micron thick TiAlN hardcoat deposited by physical vapor deposition were obtained from a vendor. The blades were plasma primed with an oxidized silane DLG layer essentially as described above. The primed blades were then coated with EGC-1720 by wiping the surface of the scissors with a cloth saturated in EGC-1720. After wiping, the coating was cured in an oven at 120° C. for 15 minutes. The resulting blades were then evaluated using the tape snap and adhesive removal test described above. After tape snapping the surface with 165 tape the EGC-1720 coating was retained and the 007A adhesive was easy to rub off.

Comparative Example Scissor Blades with Titanium Aluminum Nitride, NO Tie Layer, and Perfluoropolyether Silane

Scissor blades as described in Example 3 but without the DLG tie layer were made. They were then evaluated using the tape snap and adhesive removal test described above. Initially, they allowed the 007A adhesive to be rubbed off easily; but after tape snapping the surface with 165 tape, the EGC-1720 coating was mostly removed and the 007A adhesive was difficult to rub off.

Example 4 Scissors with Titanium Aluminum Nitride, DLG, and Perfluoropolyether Silane Triple Layers

Stainless steel scissors were made essentially as described in Example 3. The scissors were evaluated using the tape snap and adhesive removal test described above. After tape snapping the surface with 165 tape the EGC-1720 coating was retained and the 007A adhesive was easy to rub off.

Then, the scissors were used to cut an 800 inch (20.32 m) length roll of 165 tape lengthwise down the middle. No adhesive build-up was observed on the blades, demonstrating good non-stick properties.

Next, the scissors were used to cut Staples copy paper 10,000 times. Then, 007A adhesive was applied to the inside of the blades and it was still very easy to rub off, which demonstrates good durability by withstanding the abrasion of the blades rubbing/cutting the paper 10,000 times.

These scissors were then used again to cut an 800 inch (20.32 m) length roll of 165 tape lengthwise down the middle and no adhesive build-up was observed on the blades, demonstrating good non-stick properties after this durability test.

The complete disclosures of the publications cited herein are incorporated by reference in their entirety as if each were individually incorporated. Various modifications and alterations to this invention will become apparent to those skilled in the art without departing from the scope and spirit of this invention. It should be understood that this invention is not intended to be unduly limited by the illustrative embodiments and examples set forth herein and that such examples and embodiments are presented by way of example only with the scope of the invention intended to be limited only by the claims set forth herein as follows. 

1. A method of making a coated metal article comprising: (a) forming a hardcoat layer on at least a portion of a surface of a metal or metalized substrate by physical vapor deposition; (b) forming a tie layer comprising silicon, oxygen, and hydrogen on at least a portion of the surface of the hardcoat layer by plasma deposition; (c) applying an at least partially fluorinated composition comprising at least one silane group to at least a portion of the surface of the tie layer.
 2. The method of claim 1 wherein the hardcoat layer is formed by cathodic arc, sputtering, thermal evaporation, or e-beam evaporation.
 3. The method of claim 1 wherein the hardcoat layer comprises a metal nitride or a mixed metal nitride.
 4. The method of claim 3 wherein the hardcoat layer comprises at least one of titanium nitride, zirconium nitride, aluminum nitride, or titanium aluminum nitride. 5-7. (canceled)
 8. The method of claim 1 wherein forming the tie layer comprises ionizing a gas comprising at least one of an organosilicon or a silane compound.
 9. The method of claim 1 wherein the tie layer further comprises at least one of carbon, diamond-like glass, silicon oxycarbide, silicon carbide, silicon oxide, silicon dioxide, silicon nitride, or silicon oxynitride. 10-15. (canceled)
 16. The method of claim 1 wherein the at least partially fluorinated composition comprising at least one silane group is a quat silane of Formula V:

wherein b and c is each independently an integer of 1 to 3; R_(f) is a perfluorinated ether group; A is a linking group having the formula —C_(d)H_(2d)ZC_(g)H_(2g)—, wherein d and g are independently integers from 0 to 10 and Z is selected from the group consisting of a covalent bond, a carbonyl group, a sulfonyl group, a carboxamido group, a sulfonamido group, an iminocarbonyl group, an iminosulfonyl group, an oxycarbonyl group, a urea group, a urethane group, a carbonate group, and a carbonyloxy group; Y is a bridging group having 1 to 10 carbon atoms, a valency of 2 to 6, and comprising at least one of an alkylene group or an arylene group; Q is a connecting group having 1 to 10 carbon atoms, a valency of 2 to 6, and comprising at least one of an alkylene group or an arylene group; R¹ and R² are independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and an aralkyl group; each R³ is independently selected from the group consisting of hydroxy groups, alkoxy groups, acyl groups, acyloxy groups, halo groups, and polyether groups; and X⁻ is a counter ion selected from the group consisting of inorganic anions, organic anions, and combinations thereof.
 17. The method of claim 1 wherein the at least partially fluorinated composition comprising at least one silane group is a quat silane of Formula VI:

wherein R_(f) has the structure —CF(CF₃)(OCF₂CF(CF₃))_(m)OCF₂CF₂CF₂CF₂O(CF(CF₃)CF₂O)_(n)CF(CF₃)—, wherein m is an integer of 1 to 12 and n is an integer of 2 to 10; c is an integer from about 1 to about 3; A is a linking group having the formula —C_(d)H_(2d)ZC_(g)H_(2g)—, wherein d and g are independently integers from about 0 to about 10 and Z is selected from the group consisting of a covalent bond, a carbonyl group, a sulfonyl group, a carboxamido group, a sulfonamido group, an iminocarbonyl group, an iminosulfonyl group, an oxycarbonyl group, a urea group, a urethane group, a carbonate group, and a carbonyloxy group; Y is a bridging group comprising an alkylene group having about 1 to about 6 carbon atoms; Q is a connecting group comprising an alkylene group having about 1 to about 6 carbon atoms; R¹ and R² are independently alkyl groups having about 1 to about 4 carbon atoms; each R³ is independently selected from the group consisting of hydroxy groups, methoxy groups, ethoxy groups, acetoxy groups, chloro groups, and polyether groups; and X⁻ is a counter ion selected from the group consisting of a halide, sulfate, phosphate, an alkyl sulfonate, an aryl sulfonate, an alkyl phosphonate, an aryl phosphonate, a fluorinated alkyl sulfonate, a fluorinated aryl sulfonate, a fluorinated alkyl sulfonimide, a fluorinated alkyl methide, and combinations thereof.
 18. The method of claim 1 wherein the at least partially fluorinated composition comprising at least one silane group comprises hexafluoropropyleneoxide.
 19. The method of claim 1 wherein the at least partially fluorinated composition comprising at least one silane group comprises a composition comprising: (a) a first polyfluoropolyether silane of the Formula VIIa: CF₃CF₂CF₂O(CF(CF₃)CF₂O)_(p)CF(CF₃)—C(O)NH(CH₂)₃Si(Y)₃  VIIa wherein each Y is independently a hydrolyzable group and wherein p is 3 to 50; and (b) a second polyfluoropolyether silane of the Formula IIXa: (Y′)₃Si(CH₂)₃NHC(O)—CF₂O(CF₂O)_(m)(C₂F₄O)_(q)CF₂—C(O)NH(CH₂)₃Si(Y′)₃  IIXa wherein each Y′ is independently a hydrolyzable group and wherein m is 1 to 50 and q is 3 to
 40. 20. The method of claim 1 wherein the at least partially fluorinated composition comprising at least one silane group comprises a composition comprising: (a) a first polyfluoropolyether silane entity of the Formula VIIb: CF₃CF₂CF₂O(CF(CF₃)CF₂O)_(p)CF(CF₃)—C(O)NH(CH₂)₃Si(O—)₃  VIIb wherein p is 3 to 50; and (b) a second polyfluoropolyether silane entity of the Formula IIXb: (—O)₃Si(CH₂)₃NHC(O)—CF₂O(CF₂O)_(m)(C₂F₄O)_(q)CF₂—C(O)NH(CH₂)₃Si(O—)₃  IIXb wherein m is 1 to 50 and q is 3 to
 40. 21. The method of claim 1 wherein the hardcoat layer is formed using cathodic arc deposition, the tie layer is formed using ion-assisted plasma deposition, and the at least partially fluorinated composition is applied by thermal evaporation and condensation of the composition.
 22. The method of claim 21 wherein the hardcoat layer is formed, the tie layer is formed, and the at least partially fluorinated composition is applied within a single deposition chamber.
 23. The method of claim 1 wherein the metal or metalized substrate comprises stainless steel.
 24. A coated metal article comprising: (a) a metal or metalized substrate; (b) a physical vapor deposited hardcoat layer disposed on at least a portion of the metal or metalized substrate; (c) a plasma deposited tie layer comprising silicon, oxygen, and hydrogen disposed on at least a portion of the surface of the hardcoat layer; and (d) an at least partially fluorinated composition comprising at least one silane group disposed on at least a portion of the surface of the tie layer.
 25. The coated metal article of claim 24 wherein the article is a cutting tool or element.
 26. The coated metal article of claim 24 wherein the article is a kitchen or bathroom fixture or appliance.
 27. The coated metal article of claim 24 wherein the hardcoat layer comprises a metal nitride or a mixed metal nitride.
 28. The coated metal article of claim 24 wherein the tie layer further comprises carbon.
 29. The coated metal article of claim 24 wherein the at least partially fluorinated composition comprising at least one silane group comprises hexafluoropropyleneoxide. 